Determination of the Effective Redox Potentials of SmI2, SmBr2

Feb 11, 2014 - (d) Molander , G. A.; Czakó , B.; St. Jean , D. J. , Jr. J. Org. Chem. 2006, 71 ..... (c) McDonald , C. E.; Ramsey , J. R.; Sampsell ,...
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Determination of the Effective Redox Potentials of SmI2, SmBr2, SmCl2, and their Complexes with Water by Reduction of Aromatic Hydrocarbons. Reduction of Anthracene and Stilbene by Samarium(II) Iodide−Water Complex Michal Szostak,* Malcolm Spain, and David J. Procter* School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, United Kingdom S Supporting Information *

ABSTRACT: Samarium(II) iodide−water complexes are ideally suited to mediate challenging electron transfer reactions, yet the effective redox potential of these powerful reductants has not been determined. Herein, we report an examination of the reactivity of SmI2(H2O)n with a series of unsaturated hydrocarbons and alkyl halides with reduction potentials ranging from −1.6 to −3.4 V vs SCE. We found that SmI2(H2O)n reacts with substrates that have reduction potentials more positive than −2.21 V vs SCE, which is much higher than the thermodynamic redox potential of SmI2(H2O)n determined by electrochemical methods (up to −1.3 V vs SCE). Determination of the effective redox potential demonstrates that coordination of water to SmI2 increases the effective reducing power of Sm(II) by more than 0.4 V. We demonstrate that complexes of SmI2(H2O)n arising from the addition of large amounts of H2O (500 equiv) are much less reactive toward reduction of aromatic hydrocarbons than complexes of SmI2(H2O)n prepared using 50 equiv of H2O. We also report that SmI2(H2O)n cleanly mediates Birch reductions of substrates bearing at least two aromatic rings in excellent yields, at room temperature, under very mild reaction conditions, and with selectivity that is not attainable by other single electron transfer reductants.

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INTRODUCTION Since its discovery in 1977 by Kagan,1 SmI2 (samarium(II) iodide, Kagan’s reagent) has gained status as one of the most important single electron transfer reagents in organic chemistry.2 Of particular importance is the exquisite ability of SmI2 to mediate reductive processes via complementary oneand two-electron pathways with chemoselectivity that cannot be achieved by other reagents.3,4 Crucial to the successful use of SmI2 in numerous synthetic methodologies and target oriented syntheses is the role of additives that modulate the steric requirements and redox potential of the reagent by coordination to the lanthanide(II) center, thus allowing users to fine-tune the properties of SmI2 for a desired transformation (Figure 1).5 In this regard, during the past decade, SmI2(H2O)n complexes have received increasing attention as unique Sm(II) reagents capable of mediating challenging reductive processes that for years had been thought to lie outside the redox potential of SmI2.6 However, despite several reports on the role of H2O as a ligand for Sm(II),7 mechanistic details pertaining to the effective redox potential of these powerful reductants have not been investigated, hampering the development of new chemoselective reactions mediated by SmI2(H2O)n and prohibiting the rational design of ligands that would expand © 2014 American Chemical Society

Figure 1. Redox potentials of common Sm(II) reductants (SCE = saturated calomel electrode).

the chemoselectivity of Sm(II) for a broad range of functional groups.8 In general, the reactivity of Sm(II) reductants has been found to correlate with the thermodynamic redox potentials as determined by electrochemical methods (Table 1). The seminal studies by Flowers9 and Skrydstrup10 demonstrated that addition of 4 equiv of HMPA results in an increase of the redox potential of SmI2 by ca. 0.90 V (Table 1, entries 1 and 2), affording one of the most powerful reductants in organic synthesis. Due to the high redox potential, SmI2−HMPA Received: December 19, 2013 Published: February 11, 2014 2522

dx.doi.org/10.1021/jo4028243 | J. Org. Chem. 2014, 79, 2522−2537

The Journal of Organic Chemistry

Article

Table 1. Summary of Redox Potentials of Common Sm(II) Reductants Determined by Electrochemical Methods entry

Sm(II) reductant

−E1/2a

electrode

solvent

refs

1 2 3 4 5 6 7 8 9

SmI2 SmI2−HMPA SmI2−DMPU SmBr2 SmCl2 Sm(HMDS)2 SmBr2−HMPA SmI2(H2O)n (n = 60) SmI2(H2O)n (n = 500)

0.89 ± 0.08b 1.79 ± 0.08 1.61 ± 0.01c 1.55 ± 0.07d 1.78 ± 0.10e 1.5 ± 0.1f 2.03 ± 0.01g 1.0 ± 0.1h 1.3 ± 0.1i

SCE SCE SCE SCE SCE SCE SCE SCE SCE

THF THF THF THF THF THF THF THF/DME THF/DME

9, 10 9, 10 12 14b 14b 18 19 7a 7a

In volts vs SCE. −E1/2 describes the half-reduction potential measured in DMF, refs 20−23. (The accuracy is approximately ± 0.1 V due to solvent effects.) bRecalculated from −1.41 ± 0.08 vs Fe+/Fe according to ref 23. cRecalculated from −2.21 ± 0.01 vs Ag/AgNO3; the difference between the SCE and Ag/AgNO3 is 0.6 V, ref 12b. dNote that the value based on ref 14a, recalculated from −1.98 ± 0.01 vs Ag/AgNO3, is −1.38 ± 0.01 vs SCE. e Note that the value based on ref 14a, recalculated from −2.11 ± 0.01 vs Ag/AgNO3, is −1.51 ± 0.01 vs SCE. fRecalculated from −2.1 ± 0.1 vs Ag/ AgNO3. gRecalculated from −2.63 ± 0.01 vs Ag/AgNO3. hRecalculated from −1.6 ± 0.1 vs Ag/AgNO3. iRecalculated from −1.9 ± 0.1 vs Ag/ AgNO3. a

complexes have found diverse applications in Barbier reactions and reductive cross-couplings utilizing unactivated π-acceptors.11 The addition of other Lewis bases (e.g., 1,3-dimethyl3,4,5,6-tetrahydro-2-pyrimidinone (DMPU), N-methyl-2-pyrrolidone (NMP), 2,2,6,6-tetramethylpiperidine (TMP), tripyrrolidino-phosphoric acid triamide (TPPA)) has been reported to increase the thermodynamic redox potential of SmI2 (Table 1, entry 3);12 however, despite significant progress in this area,13 HMPA is currently the most effective Lewis basic additive for SmI2. Furthermore, Flowers has shown that the addition of 12 equiv of metal salts, LiBr or LiCl, to SmI2 results in the formation of soluble Sm(II) reductants characterized by redox potential much higher than that of the parent reagent (Table 1, entries 4 and 5).14 UV−vis experiments demonstrated that this reagent combination is equivalent to the less soluble SmBr2 and SmCl2 prepared by independent methods by the reduction of SmX3.15 Recently, SmBr216 and SmCl217 reductants have been applied to achieve cross-coupling reactions of carbonyl precursors in complex settings. The thermodynamic redox potentials of SmI2(HMDS)218 and SmBr2−HMPA19 have also been reported (Table 1, entries 6 and 7) and, as expected, are much higher than those of SmI 2 and SmI 2 −HMPA, respectively. Finally, in 2004, Flowers reported a seminal study on the thermodynamic redox potential of SmI2(H2O)n (Table 1, entries 8 and 9).7b It was found that the addition of 60 equiv of water with respect to SmI2 results in an increase of redox potential of SmI2 by ca. 0.10 V. The addition of 500 equiv of water resulted in the formation of a thermodynamically more powerful reductant (redox potential of 1.3 V vs SCE). Further addition of water had no additional impact on the redox potential of the reagent. Studies on the determination of the effective redox potential of lanthanide reductants have also been reported (Table 2).20−24 These methods utilize the reduction of a series of aromatic hydrocarbons with gradually increasing redox potentials to correlate the reactivity of a lanthanide reductant with the reduction potential of hydrocarbons. This indirect determination of the redox potential is particularly useful in cases of limited solubility, irreversible oxidation, precipitation, and/or instability of lanthanide reductants under the conditions of cyclic voltammetry studies. More specifically, Chauvin determined the effective redox potential of several lanthanides(0) (Ce, Nd, Sm, Yb) (Table 2, entries 1 and 2),20 Evans demonstrated that decamethylsamarocene, Sm(C5Me5)2, is one

Table 2. Summary of Redox Potentials of Common Ln(II) Reductants Determined by Reduction of Aromatic Hydrocarbons entry

Ln(II) reductant

−E1/2a

electrode

solvent

ref

1 2 3 4 5 6 7

Sm metal Yb metal Sm(C5Me5)2 TmI2(THF)n YbI2−amine−H2O SmI2−amine−H2O TmI2(MeOH)n

2.02 2.44 2.22 2.00 2.30 2.80 2.65

SCE SCE SCE SCE SCE SCE SCE

DME DME toluene THF THF THF THF

20 20 21 22 23 23 24

a In volts vs SCE. −E1/2 describes the half-reduction potential measured in DMF, refs 20−23. (The accuracy is approximately ± 0.1 V due to solvent effects.)

of the strongest lanthanide(II) reductants reported to date (Table 2, entry 3),21 Fedushkin evaluated the reducing power of TmI2 (Table 2, entry 4),22 Hilmersson determined the redox potential of the powerful SmI2−amine−H2O and YbI2−amine− H2O systems (Table 2, entries 5 and 6),23 and we have utilized this method to show that the reagent formed by complexation of MeOH to TmI2 is characterized by a much higher redox potential than the parent lanthanide(II) iodide (Table 2, entry 7).24 Importantly, since only simple unsaturated hydrocarbons, which react via a well-established, outer-sphere electron transfer mechanism, are used,8,14b,18,23 these methods provide a robust and practical evaluation of the effective reducing power of a given lanthanide reductant under standard laboratory reaction conditions, thus allowing definition of a practical reactivity scale in an assay independent of the thermodynamic redox potential measurements. Our laboratory has pioneered the use of SmI2(H2O)n complexes to expand the reactivity of SmI2 toward carbonyl functional groups traditionally thought to lie outside the reducing range of Kagan’s reagent (Scheme 2).25−27 In particular, we reported that activation of SmI2 with water permits a fully chemoselective reduction of six-membered lactones over other classes of lactones and esters (Scheme 2A).25a−c Moreover, we exploited the SmI2(H2O)n reagent to develop the first chemoselective monoreduction of cyclic diesters (Meldrum’s acids) to afford the valuable β-hydroxy acid building blocks in a single transformation (Scheme 2B).26 Recently, we utilized the unusual ketyl-type radical intermediates formed in SmI2(H2O)n-mediated electron transfer to 2523

dx.doi.org/10.1021/jo4028243 | J. Org. Chem. 2014, 79, 2522−2537

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Moreover, we describe herein the synthesis and determination of the effective redox potential of several reductants related to SmI2, namely, SmX2 and SmX2(H2O)n (X = Cl, Br),16,17 which allows us to delineate the reducing power of these popular Sm(II) reductants for the first time. Furthermore, as a result of this investigation, we report that SmI2(H2O)n cleanly mediates Birch reduction33 of substrates with at least two aromatic rings in excellent yields, at room temperature, under very mild reaction conditions, and with selectivity that is not attainable by other single electron transfer reductants.3,4 Finally, we provide mechanistic studies into the role of electron transfer from Sm(II) and discuss the implications of the effective redox potentials as determined in this study for using SmX2 and SmX2(H2O)n complexes in organic synthesis. This study provides the first set of guidelines with respect to reducing power to further our understanding of single electron transfer processes mediated by the extremely useful Sm(II)based reductants.

lactone carbonyls as precursors in complex cyclization and cyclization cascade processes to form polyoxygenated azulene motifs (Scheme 2C).25c,d We have also established that water serves a critical role with Sm(II) in the first general reductions of unactivated aliphatic esters, acids, and lactones with SmI2, which proceed via acyl-type radical intermediates generated directly from the carboxylic acid derived functional groups.27 These processes have resulted in very significant expansion of the synthetic scope of processes mediated by SmI2.28 A subtle feature of all of these reactions is that water serves as a unique additive for SmI2; no reaction occurs with SmI2 alone or with a variety of other additives (e.g., HMPA, DMPU, LiCl), which have been shown to form more thermodynamically powerful complexes with SmI2 than SmI2(H2O)n (Table 1). Furthermore, we established that no reaction occurs at low concentration of water, which rules out the role of water as a proton donor placed in a close proximity to the radical anion after the electron transfer step.29

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RESULTS AND DISCUSSION To determine the effective redox potential of SmI2(H2O)n complexes, we selected a series of aromatic hydrocarbons with reduction potentials ranging from −1.6 to −3.4 V vs SCE (Figure 3).20−24 In addition, a series of alkyl halides (E1/2 from

Figure 2. Recent applications of SmI2(H2O)n in chemoselective and stereoselective synthesis: (A) reduction of six-membered lactones; (B) monoreduction of Meldrum’s acids; (C) cyclization cascades of lactones. Figure 3. Structures of aromatic hydrocarbons and alkyl halides used in this study together with their half-reduction potentials (E1/2 in volts in DMF vs SCE).

On the basis of our extensive experience in the reductive chemistry of lanthanides(II), we considered that the reduction of lactone carbonyls (E1/2 = ca. −3.0 V vs SCE)30 by SmI2(H2O)n (E1/2 = ca. −1.3 V vs SCE)7b is inconsistent with the thermodynamic redox potential of SmI2(H2O)n as determined by cyclic voltammetry studies and cannot be explained exclusively by electrostatic interaction31 between the lactone carbonyl groups and the Lewis acidic Sm(II) center.32 To understand in more detail the properties of SmI2(H2O)n reductants, we determined the effective redox potential of these reagents by examining the reactivity of SmI2(H2O)n complexes with a series of unsaturated hydrocarbons and alkyl halides with reduction potentials ranging from −1.6 to −3.4 V vs SCE. Remarkably, we found that SmI2(H2O)n reacts with substrates which have reduction potentials more positive than −2.21 V vs SCE, which is much higher than the thermodynamic redox potential of SmI2(H2O)n determined by electrochemical methods (up to −1.3 V vs SCE).7b Moreover, in contrast to literature, we demonstrated that complexes of SmI2(H2O)n in which n = 500 are much less reactive toward aromatic hydrocarbons than complexes of SmI2(H2O)n based on n = 50.7 This has important practical implications for using SmI2(H2O)n reagents in organic synthesis.

−1.30 to −3.0 V)34 was selected for this study to gain further insight into the chemoselectivity of SmI2(H2O)n mediated reactions. These substrates are well-established to react via an outer-sphere mechanism10a,14b,18,23,28o,p and should provide complementary information on the effective reducing power of SmI2(H2O)n to the reactions with a set of aromatic hydrocarbons. We started our investigation by studying in detail the reduction of aromatic hydrocarbons using SmI 2 (H 2 O) n complexes in which n = 50 and n = 500 with respect to SmI2 because these complexes have been shown previously to be more thermodynamically powerful than the parent SmI2 (Table 3).7b In order to determine the increase of effective redox potential upon coordination of H2O to Sm(II), the reduction by SmI2 in THF was chosen as a benchmark. For comparison, all runs were performed in parallel, using stock solutions of SmI2 prepared immediately prior to use35 and titrated according to the established methods to determine the molarity of the active Sm(II) reductant.35d,e All reactions were performed with 3 equiv of Sm(II) reductant (1.5 molar 2524

dx.doi.org/10.1021/jo4028243 | J. Org. Chem. 2014, 79, 2522−2537

The Journal of Organic Chemistry

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Table 3. Determination of Redox Potential of SmI2(H2O)n by Reduction of Aromatic Hydrocarbons reaction with SmI2(H2O)n entry

hydrocarbon

−E1/2a

reaction with SmI2

n = 50

n = 500

1 2 3 4 5 6 7 8 9 10

acenaphthylene cyclooctatetraene anthracene diphenylacetylene stilbene 1,4-diphenylbenzene 1,3,5-triphenylbenzene naphthalene styrene benzene

1.65 1.83 1.98 2.11 2.21 2.40 2.51 2.61 2.65 3.42

52.6 (6 h) >98 (6 h)